Acid amide derivatives of azo-dyestuffs



ACID Al\/1H)E DERIVATIVES OF AZO-DYESTUFFS Max Schmid, Riehen, Eduard Moser, Basel, Jakob Danuser, Arlesheim, Rudolf Mory, Binningen, Willy Mueller, Riehen, and Jakob Wuergler, Neuewelt, near Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Application October 19, 1953,

Serial No. 387,067

Claims priority, application Switzerland October 20, 1952 8 Claims. or; 260-174) The present application is a continuation-in-part of our co-pending application Serial No. 273,364 filed February 25, 1952. v

The present invention provides new acid amide derivatives of azo-dyestuffs whichare free from sulfonic acid groups and correspond to the general formula in which R1 and R2 each represent the radical of a diazocomponent, X stands for hydrogen or an alkyl group of low molecular weight and is the radical of a non-vattable diamine, at least one of f the radical R1 or R2 containing a trifluoromethyl group.

These acid amide derivatives are advantageously prepared by condensing two molecularproportions of a halide of the formula H? (JG-halogen or one molecular proportion of two different halides of the formulae v I (3) H? C -helogen and halogen-(KI! on The meanings of R1, R2, R3 and X in Formulae 3 to 5 are the same as given in the first paragraph. I

United States Patent '0 The acid halides can be obtained by treating the appro- 7 priate carboxylic acids with acid halogenizing agents. These carboxylic acids of the formulae and H000 OH can in turn be prepared by methods in themselves known by coupling diazo compounds free from sulfonic acid groups with 2-hydroxynaphthalene-3-carboxylic acid, diazo components containing trifluoromethyl groups being used at least for the prepartion of the products of Formula 6.

The diazo-components can belong preferably to the benzene series. The following compounds may be mentioned as examples:

1-amino-2-chloro-5 -trifluoromethyl-benzene, 1-amino-2-trifiuoromethyl-4-chlorobenzene, 1-amino-3 S-ditrifluoromethyl) -benzene, 1-amino-S-trifiuoromethyl-benzene-2-ethyl-sulfone.

When according to the present invention the acid amide derivatives are of an asymmetrical constitution, i. e. are prepared by condensing a diamine of the Formula 5 with an acid halide of each of the Formulae 3 and 4, there may be used for the preparation of compounds of the Formula 7 yielding an acid halide of the Formula 4 also diazo-components free from trifluoromethyl groups, preferably those which are suitable for the preparation of ice-colors.

The azo-compounds of Formulae 6 and 7 containing carboxylic acid groups are treated with agents capable of forming acid halides. As such agents there are to be understood those which are capable of converting carboxylic acids into their acid halides, for example their bromides or chlorides: there are especially suitable as such agents phosphorus halides, phosphorus pentabromide or phosphorus trichloride, phosphorus pentachloride and phosphorus oxy-halides. It is of advantage to choose acid-chlorinating agents, i. e. those which serve for the preparation of the appropriate acid chlorides such as phosphorus pentachloride and thionyl chloride.

The treatment with such halogenating agents is advantageously carried out in an inert organic solvent, such as dimethylformamide, a chlorobenzene, for example, monoor dichlorobenzene, toluene, xylene, benzene or nitrobenzene.

In preparing such acid halides it is generally of advantage first to dry the azo-compound produced in an aqueous medium or to free it from water by azeotropic distillation in an organic solvent. This azeotropic drying may, if desired, immediately precede the treatment with the halogenating agent.

As diarnines of Formula 5 there are advantageously used those whose amino groups are both bound to aromatic carbon atoms, for example those in which R3 represents an aromatic radical of the naphthalene or benzene series, in which the amino groups may be primary or, if desired, secondary. The diarnines can be mononuclear, such as for example, 1:4-diarninobenzene, -l:4-diamino-2-chlorobenzene, 1:4-diamino-2:5 dialkoxybenzene or 1:4-diaminobenzenes, having in the Z-andS-position various substituents such as nitro-, halogen atoms, alkoxy groups, alkyl groups. I

As a rule particularly valuable results are obtained 3 Whe'ndi-atnd polynu'clear'amines are used, as, for instance, when 4r4"--diamino-diphenyl and its derivatives such as for example 3:3'-dichloro-, .3:3'-dimethyl-, 3:3'-dialkoxy- 4:4-diamino-diphenyl, 3 5 :3 5'tetrachloro-4:4-diaminodiphenyl and :5 :3 5 tetramethylt 4'-diamino-diphenyl.

In many cases valuable dyestuffs are also obtained by using diamines of? the benzene series in which two identical or different benzene nuclei are linked together by a suitable bridge member, for example, by oxygen, or an SOzgroup, as in-the case for example of 4:4'-diamino-diphenyl-sulfone, 3:3' -diarnino 4:4- dichloro diphenyl sulfone, 3 3"'--diamino-4:4-dimethoxy-diphenylsulfone, or a CO group such as for example 3 13'- diamino-diphenyl-ketone, 3 :.3-diamino-4:4'-dichloro diphenyl-ketone, 3 :3 -diamino-4 4'-dimethoxy-diphenyl-ketone, or a CHr-group such as for example 3:3-diamino-diphenyl-methane, 3 i3- diamino-4:4- dichloro-diphenyl-methane, 4:4'- diami'no 3:3'- dichloro diphenylrnethane, 4:4- diamino 3 55.1325 tetrachloro-diphenylm'ethane, or the groups -NHCO, NHCONH-,

'Finallythere-come into consideration diamines of quite a difierent kind, for example, 2:8-diamino-chrysene, 4:11- dhmino-fluor'oanthene, 2:6- or 1:5 diamino-naphthalene.

ln addition diarnines with secondary amino groups can also be used, advantageously di-(N-alkylamino)-aryl compounds such as 4:4-di-(methylamino)diphenyl or 4 4-di- (methylamino diphenyl-sulfone.

The condensation of the carboxylic acid halides described above with the diamines is advantageously carried out in'ana'rihydrous medium. Under these conditions the condensation generally proceeds surprisingly easily even 'at temperatures within the range of the boiling points ofinormal organic solvents such as toluene, "'moriochlorobe'nzene, dichlorobenzene, trichlorobenzene, nitrobe'nzene a'nd thelike. In order to accelerate the reaction 'it-is generally desirable toremove the'hydro- '-'-'clil'oric acid-obtained during condensation, for example by continuousdistillatiomboiling underrefiux-or by add- -in'g an-acid binding agent 'suchas anhydrous sodium acetate, pyridine or anhydrous ammonia. The dyestuffs so-obtained arein-part crystalline:and in part amorphous, 'a'nd are generallyobtained in very good yieldrand in purestate. -Itmay be of advantage, in order to produce especially pure'dyestufis, first to isolate the acid chlorides obtained from the carboxylic acids, and if desired, to *recrystallize'theacid chlorides. In some cases, however, the' isola'tio'nof'theacid chloride may be dispensed with without any harmful effects andinsome cases with an improvement -eve'n 'in'the result, and the condensation carried out immediately following the preparation of the -"-adl:tesives, such-as casein, *hardenable plastics, especially u'rea' ormelamine-formaldehyde condensation products, polyvinyl chloride -or polyvinyl acetate solutions or zride with very good fastness properties.

or water-in-oil emulsions) on a substratum, especially on textile .fibers .butalso on .other flat shaped structures such as paper (for example wall-papers) or fabrics made of glass fibers. The pigments can also-be used for other purposes, for example, .in ,a finely dispersed form for dyeing artificial silk made of'viscose or cellulose ethers or esters or superpo'lyamides or superpolyurethanes in the spinning solution, and also serve well in the manufacture of colored iakesorfiake'formers, solutions and products made of 'acetyl cellulose, 'nitro-rcellu'lose, natural resins such as polymerization .orcondensation resins, for example, aminoplasts, phenoplasts, polystyrene, polyethylene, polyacryl, rubber, casein, silicones and silicone resins. They *can also be used with advantage in the manufacture of colored pencils, cosmetic preparations and laminated :plates.

By virtue of the especially favorable physical form in which the products er the invention are generally obtained, and owing to their chemical inertness and good temperature resistance, they can 'usually be dispersed easily in 'masses or preparations of the aforesaid kind, and advantageously at a stage at which these masses or preparations have not yet'reac'hed their final shape. The

:limiting its scope inany way. Theparts and percentages are by weight unless otherwise stated.

Example 1 78.9 parts of the dyestuif from diazotized l-amino- 2-chloro5-trifluoromethyl-benzene and 2-hydroxy-naph- .thalene-3-carboxylic acid are suspended in 800 parts by volume of dry toluene; 28.6 parts of thionly chloride are added andathe wholeis slowlyheatedtto the boiling point of the-solvent. As-scones the whole has completely dissolved, the reaction :mixture. is maintained for a short timeatza gentle'xboil. Aftercooling, the whole is filtered with suction and washed with toluene. The orange colored crystals of the acid chloride melt at 216 to 217 C. (uncorrected).

41.3 parts of the acid chloride are dissolved hot in 500 parts by volume of anhydrous -toluene. A solution of 5.4 parts of lz4-diaminobenzene in 50 parts by volume of dry pyridine is added and the whole is maintained at a gentle boil while stirring "for 15 hours. The pigment formedisfiltered with .suction while hot and washed thoroughly with hot toluene and then dried in vacuo at 60 to 65 C. The dyestuff of the formula l C l is an orange colored powder. It colors polyvinyl chloride and other plastics brilliantred-orange tints with good fastness properties.

By using, instead of 1:4-diamino-benzene, 1:4-diarnino- Z-chlorobenzene in the condensation there is obtained a somewhat redder orange. coloration in the polyvinyl chlo With 4:4- diamino-diphenyl-sulfone there is obtained a yellow orange "color, with-'4r4 diaminoe1 L'adiphenyl urea. ared orange and with 4:4'-diamino-2-methoxy-5methyl-1:1 azobenzene a scarlet'color;

'Example 2 39%45 partsroftthe'dyestufiifrom .diazotized. 1-3131 3072- emulsions or other emulsions (for example oil-.in-water chlorotrifiuoromethyl benzene :tand 2-hydroxy-naphand then dried at 45 C. in vacuo.

thalene-3-carboxylic acid are stirred well in 280 parts by volume of anhydrous chlorobenzene, and 14.3 parts of thionyl chloride are added. The whole is slowly heated to the boiling point of the solvent and maintained at the boil for about half an hour. 126 parts of 3:3'-dich1oro- 4:4diamino-diphenyl dissolved in 50 parts by volume of warm chlorobenzene and parts by volume of pyridine are added to the solution. The reaction mixture is maintained at the boil for hours, is filtered otf while hot and Washed with hot chlorobenzene until the washings are almost colorless. The dyestufi is dried at 65 C. in vacuo. It colors polyvinyl chloride reddish orange tints which have an excellent fastness to migration and very good fastness to light. The pigment is very suitable for pigment-printing and for dyeing acetate silk in the spinning solution.

If instead of 3:3'dichl0ro-4:4-diamino-diphenyl, other diamines are used in the condensation, for example 4:4'-diamino-diphenyl, 3 3-dimethyl-4 4'-diaminodiphenyl, 1:5-diamino-naphthalene, 4:4-diamino-diphenyl-methane, there are obtained dyestufi's of a similar shade with very good fastness properties, especially in various plastics.

Example 3 85.6 parts of the dyestufi from diazotized 1-a1nin0-325- di-(trifiuoromethyl)-benzene and Z-hydroxy-naphthalene- 3-carboxylic acid are stirred in 500 parts by volume of anhydrous toluene; 28.6 parts of thionyl chloride are added and the whole heated to the boil. After complete dissolution, the whole is maintained at the boil for a further half hour, any impurities filtered off hot, and the filtrate allowed to stand for some time. The crystals formed in the filtrate are filtered OE and Washed by suction filtering The acid chloride crystallizes in the form of long needles.

44.65 parts of the acid chloride are dissolved hot in 500 parts by volume of dry toluene. 10.6 parts of 3:3- dimethyl-4:4-diaminodiphenyl dissolved in 100 parts by volume of toluene and 30 parts by volume of dry pyridine are rapidly run into the solution. The formation of the dyestuff is completed by boiling for about 15 hours under reflux. The whole is filtered hot and the filtrate washed thoroughly with hot toluene. After drying there is obtained a finely crystalline dyestufi which colors plastics, for example polyvinyl chloride, orange tints having very good fastness properties.

When the above acid chloride is condensed in the same manner as described in this example with other diamines, for example, 1:4-diaminobenzene, 4:4-diamino-diphenyl, 3 :3'-dichloro-4:4-diamino-diphenyl, 1 :S-diamino-naphthalene, 3:3'-dichl0ro-4:4'-diamino-diphenyl-methane, or di-( 3-amino 4-chlorobenzoyl) -a ,S-diamino-ethane, there are obtained pigments of similar shades. With 4:4'-diamino-stilbene a brown pigement is obtained.

Example 4 47.0 parts of the acid chloride of the dyestuif from diazotized 1-amino-S-trifiuoromethyl-phenyl-Z-ethyl-sulfone and 2-hydroXy-napthalene-3-carboxylic acid which was obtained in the same manner as described in Example 1, is condensed in ortho-dichlorobenzene with 7.9 parts of 1:5-diamino-naphthalene. Condensation is carried out in the same way as described in Example 1. A brilliant yellow orange is obtained which colors plastics, especially polyvinyl chloride foils, with good fastness properties. A similar dyestuff is obtained when 3:3'-di- HO O 0- 6 methyl-4:4'-diamino-diphenyl is used instead of 1:5-diamino-napthalene.

Example 5 The dyestuif from diazotized l-amino-Z-trifluoromethyl- 4-chlorobenzene and 2-hydroxy-napthalene-3-carboxylic acid is reacted with thionyl chloride in anhydrous toluene. Brilliant red colored crystals melting at 189 to 190 C. (uncorrected) are obtained.

When reacting this acid chloride with 4:4-diaminodiphenyl in the way described in Example 3, a dyestuti is obtained in the form of a brownish powder which dissolves brilliant red in sulfuric acid. Polyvinyl chloride is colored scarlet and the dyeings have a very good fastness to migration. A similarly fast dyestuif is obtained by using 1:4-diamino-benzene instead of 4:4'diamino-diphenyl. With 2:2'-diamino-4:4-dichloro-diphenyl sulfide an orange tint is obtained, and with the diarnine of the formula r HzNOSOz-N-OrS-ONH:

a scarlet shade.

What is claimed is: I

1. An acid amide derivative of an azo dyestufi, which derivative is free from sulfonic acid groups and corresponds to the formula in which R1 and R2 each represent the radical of a diazocomponent of the benzene series, at least one of these radicals containing a trifiuoromethyl group, and R3 represents the radical of a non-vattable aromatic carbocyclic compound.

2. An acid amide derivative of an azo dyestutf, which derivative is free from sulfonic acid groups and corresponds to the formula 0 C O-EN-Ra-NH-O C O in which R1 represents an aromatic radical of the benzene series containing at least one trifiuoromethyl group, and R3 represents a member selected from the group consisting of a benzene radical and a diphenyl radical.

4. The acid amide derivative of the formula -oo on or,

5. The acid amide derivative of the formula m0 HO 0 O-ENO-NH-eO? 6. The aeid,amide den'vative of the formula 30 CO-HN "IheI-acidfimide derivative of formula GFs 8. The acid afnide derivative of the fqrmula I FaC No references cited. 

1. AN ACID AMIDE DERIVATIVE OF AN AZO DYESTUFF, WHICH DERIVATIVE IS FREE FRO SULFONIC ACID GROUPS AND CORRESPONDS TO THE FORMULA 